CN103665788A - Modified PET copolyester and preparation method and application thereof - Google Patents
Modified PET copolyester and preparation method and application thereof Download PDFInfo
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- CN103665788A CN103665788A CN201310628445.XA CN201310628445A CN103665788A CN 103665788 A CN103665788 A CN 103665788A CN 201310628445 A CN201310628445 A CN 201310628445A CN 103665788 A CN103665788 A CN 103665788A
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Abstract
The invention belongs to the technical field of polyester preparation, and discloses a modified PET copolyester with high viscosity and a low terminal carboxyl group and a preparation method and application thereof. The copolyester contains the following ingredients in parts by weight: 100 parts of low-viscosity PET copolyester, 0.8-2.0 parts of oxazoline compound and 0.6-2.0 parts of a hydroxyl chain extender. The method prepares the high-viscosity modified PET copolyester by adding the oxazoline compound and the hydroxyl chain extender. The oxazoline compound is added to react with the terminal carboxyl group in resin, the terminal carboxyl group content of resin is reduced, therefore, the hot water resisting performance of resin is increased. The hydroxyl chain extender is added, the molecular weight of resin is increased, and the balance between a physical performance and a processing performance is achieved. The viscosity and the melt strength of the modified PET copolyester are increased, the content of terminal carboxyl group is reduced, and the hot water resisting performance is greatly increased. Moreover, the production method shortens the polycondensation time and the production cycle, effectively reduces the thermal degradation reaction, and also increases the output of equipment.
Description
Technical field
The invention belongs to polyester preparing technical field, particularly modified PET copolyesters of a kind of high viscosity, low terminal carboxy and its preparation method and application.
Background technology
The annual whole world has the polyester plastics goods of counting with ten million ton be discarded in refuse tip or incinerate.Polyester is abandoned or burned for environment and be harmful to.Therefore, preparing Biodegradable polyester, to replace traditional polyester be the effective way addressing the above problem.The PET copolyesters being formed by terephthalic acid, hexanodioic acid, ethylene glycol copolymerization is owing to having good biological degradability, and lower production cost, good mechanical property and processing characteristics, be subject to paying close attention to widely.
PET copolyesters mainly obtains by esterification, the polycondensation of high temperature high vacuum.In the later stage of polyreaction, it is large that material viscosity becomes, and small molecules is in melt internal diffusion difficulty, expect the copolyesters of high molecular, need in polycondensation vessel, stop the longer time, can cause like this generation of DeR, cause color of resin flavescence, end carboxyl to raise, product properties is declined.Chinese patent CN200710177236.2 discloses the two hexanolactam coupling chain extension legal systems of a kind of Er of utilization Yuan oxazoline and diacyl for the method for high viscosity poly adipate succinic acid ester; the method can be prepared the resin that viscosity is 1.1dL/g; but in the method, the two hexanolactams of diacyl can produce micromolecular compound in chain extension; make the performance degradation of resin; and the two hexanolactam prices of diacyl are higher, are unfavorable for suitability for industrialized production.
Summary of the invention
For the shortcoming that overcomes above-mentioned prior art is with not enough, primary and foremost purpose of the present invention is to provide the modified PET copolyesters that a kind of high viscosity, low terminal carboxy content, hot water resistance can be good.
Another object of the present invention is to provide the preparation method of the modified PET copolyesters that a kind of above-mentioned high viscosity, low terminal carboxy content, hot water resistance can be good.
Still a further object of the present invention is to provide the application in engineering plastics, wrapping material of modified PET copolyesters that above-mentioned high viscosity, low terminal carboxy content, hot water resistance can be good.
Object of the present invention realizes by following proposal:
High viscosity, low terminal carboxy content, hot water resistance can be good a modified PET copolyesters, comprise following component by weight:
100 parts of low viscosity PET copolyesters;
0.8～2.0 part of oxazoline compounds;
0.6～2.0 part of hydroxyl chainextender.
Described low viscosity PET copolyesters is polyethylene terephthalate-co-ethylene glycol adipate(EGA).
Preferably, in described polyethylene terephthalate-co-ethylene glycol adipate(EGA), the weight ratio of polyethylene terephthalate unit and polyethylene glycol adipate unit is (0.8～1.0): 1.
The limiting viscosity of described low viscosity PET copolyesters is 0.6～0.8dL/g.
Suo Shu oxazoline compounds is 2,2-pair-2-oxazoline, 1, at least one in two (2-oxazolinyl) benzene of 3-and 2-oxazolinyl benzene.
Described hydroxyl chainextender is at least one in isocyanate ester compound and derivative, Racemic glycidol ether compound and Racemic glycidol ester compound.
Described isocyanate ester compound comprises at least one in the vulcabond of the dimer of vulcabond, the tripolymer of vulcabond and Carbodiimide-Modified.
Preferably, at least one in described vulcabond nail phenylene diisocyanate, '-diphenylmethane diisocyanate, mphenylenedimethylim-vulcabond, isofoer diisocyanate, hexamethylene diisocyanate and the '-diphenylmethane diisocyanate that contains carbodiimide.
Described Racemic glycidol ether compound is the multipolymer that contains methyl propenoic acid glycidyl ether structure.
Described low viscosity PET copolyesters is prepared by following methods:
Terephthalic acid or dimethyl terephthalate (DMT), ethylene glycol and catalyzer are dropped in reactor, and reacting by heating, adds 1,6-hexanodioic acid to continue reaction, obtains carboxylate; Intensification step-down, polycondensation 1～3h, extrudes, and through water-cooled, tie rod, pelletizing, obtains low viscosity PET copolyesters.
Described catalyzer is at least one in antimony compounds and titanate ester compound.
Described antimony compounds comprises at least one in antimonous oxide, antimony glycol and antimony acetate.
Described titanate ester compound comprises at least one in butyl (tetra) titanate, iso-butyl titanate and isopropyl titanate.
The condition of described reacting by heating is 180～210 ℃ of esterifications.
Preferably, in order to control better esterification process, water or the methyl alcohol amount of slipping out that can generate by observing esterification, take and reach theoretical value as terminal.
Described intensification step-down refers to Heating temperature to 230～270 ℃, reduces pressure to 60Pa.
In polycondensation process, in order to reduce unnecessary DeR, can add a small amount of stablizer, comprise phosphoric acid ester stablizer, phosphorous acid esters stablizer, Hinered phenols stablizer, amine stablizer etc.
The present invention also provides the preparation method of the modified PET copolyesters that a kind of above-mentioned high viscosity, low terminal carboxy content, hot water resistance can be good, comprise following concrete steps: low viscosity PET copolyesters, oxazoline compounds, hydroxyl chainextender are dropped in twin screw extruder after mixing in mixing machine, in 200～240 ℃ melt extrude, tie rod, pelletizing, obtain the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good.
You selection of land ， oxazoline compounds can add with the form of body, also can add with the form of master batch.Wherein, count by weight, 100 Fen oxazoline compounds master batch Zhong ， oxazoline compounds content are 10～30 parts.
Above-mentioned a kind of high viscosity, low terminal carboxy content, hot water resistance can be good the application of modified PET copolyesters in engineering plastics, wrapping material.
Mechanism of the present invention is:
The present invention prepares high viscosity modified PET copolyesters by Tian Jia oxazoline compounds and hydroxyl chainextender, improve viscosity and the melt strength of resin, reduce content of carboxyl end group, improved greatly the hot water resistance energy of resin, and contribute to reduce the polycondensation time, shorten the production cycle, thereby effectively reduce thermal degradation reaction.
In the present invention, the effect of Jia Ru oxazoline compounds be mainly with resin in end carboxyl reaction, reduce the content of carboxyl end group of resin, thereby improve the hot water resistance energy of resin.Add-on, lower than 0.8 weight part, is fallen the DeGrain of low terminal carboxy, and higher than 2.0 weight parts, excessive oxazoline compounds can remain in copolyesters, affects on the one hand the mechanical property of copolyesters, can separate out resin surface on the other hand, affects product appearance.
In the present invention, add the hydroxyl chainextender of appropriate amount, the molecular weight that can improve resin, to suitable level, reaches the balance of physicals and processing characteristics.Add-on is lower than 0.6 weight part, chain extension DeGrain, and add-on, higher than 2.0 weight parts, easily causes that excessive branching is crosslinked, is unfavorable for processing.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) modified PET copolyesters of the present invention, viscosity and melt strength are improved, and content of carboxyl end group reduces, and has improved greatly the hot water resistance energy of resin.
(2) in preparation method's process of the present invention, the material high-temperature residence reaction times is short, can effectively reduce thermal degradation reaction; Production cycle shortens, and improves the production capacity of equipment.
(3) in preparation method of the present invention, resin reduces in polycondensation phase viscosity, is conducive to deviating from of ethylene glycol, can augmenting response still charging capacity.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
The reagent source using in the following example is as follows:
Dimethyl terephthalate (DMT): Japanese Supreme Being people;
Ethylene glycol: Maoming Petrochemical;
Hexanodioic acid: Liaoning petrochemical industry;
Hydroxyl chainextender ADR-4370S and ADR-4300: BASF;
Oxazoline compounds and isocyanate ester compound are commercially available analytical pure.
The testing method of product performance:
Limiting viscosity: with phenol 60%(wt)-1,2-dichlorobenzene 40%(wt) be solvent, probe temperature is 25 ℃, with Ubbelohde viscometer, records.
Content of carboxyl end group: by resin dissolves at chloroform 70%(wt)-ortho-cresol 30%(wt) in, concentration is 2g/100mL, with potentiometric titrator test, titrating solution is 0.04mol/L KOH ethanolic soln.
Melt flow rate (MFR): press GB/T3682 and measure, probe temperature is 210 ℃, loads as 2.16Kg.
Hot water resistance energy: resin is immersed in the distilled water of boiling after 24h, after 80 ℃ of oven dry, the melt flow rate (MFR) of test copolyesters.Melt flow rate (MFR) before and after boiling distillated water soaks is designated as respectively MF0 and MF1, characterizes the hot water resistance energy of resin with the ratio of MF1/MF0.The ratio of MF1/MF0 is less, represents that the hot water resistance of resin can be better.
In copolyesters, polyethylene terephthalate unit passes through with polyethylene glycol adipate unit weight ratio
1h NMR measures, with CDCl
3for solvent, with VARIAN company, produce the test of Mercury-Plus300 nuclear magnetic resonance spectrometer.Polyethylene terephthalate unit calculates by following formula than (T/A) with polyethylene glycol adipate unit weight:
T/A=(192*S
δ8.1)/(172*S
δ2.3)
S wherein
δ 8.1and S
δ 2.3for
1the integral area at 8.1ppm and 2.3ppm place in H NMR spectrogram, 192 and 172 are respectively the molecular weight of ethylene glycol terephthalate unit and ethylene glycol adipate(EGA) unit.
Synthesizing of low viscosity PET copolyesters:
By dimethyl terephthalate (DMT) 1.94Kg, ethylene glycol 2.5Kg, adds in 20L reactor, passes into high pure nitrogen 10 minutes, removes the oxygen in reactor.Be heated to 170 ℃ of interior temperature, open and stir, add 2g tetrabutyl titanate catalyzer, in 2 hours, be warming up to gradually 200 ℃, add hexanodioic acid 1.43Kg, continue reaction 1 hour.Add 2g antioxidant 1010 and 2g butyl (tetra) titanate catalyzer, be warming up to gradually 210 ℃, open vacuum pump and in reactor, set up vacuum, 30 minutes by the pressure decreased in reactor to 60Pa, and be warming up to gradually 250 ℃.Continue reaction 2 hours.After stopping stirring, in reactor, pour high pure nitrogen, product obtains low viscosity copolyesters P1 after tie rod, water-cooled, pelletizing.
According to above-mentioned steps, by table 1 formula, feed intake, obtain the low viscosity copolyesters P2～P9 of different T/A content, detect its limiting viscosity and content of carboxyl end group, the results are shown in Table 1.
Formula and the performance index of table 1 low viscosity copolyesters
The preparation of oxazoline compounds master batch: (with 2,2-two-2-oxazoline is for example)
By 2,2-two-after 2-oxazoline 3Kg and polyethylene terephthalate-co-polyethylene glycol adipate 7Kg mix in high-speed mixer, drop in twin screw extruder, extruder temperature is 140～160 ℃.The pelletizing ， get oxazoline compounds master batch through extruding, after tie rod, water-cooled.
Embodiment 1: the preparation of the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good
By 1Kg P1, after 20g2-oxazolinyl benzene, 6g hexamethylene diisocyanate mix in high mixer, drop in twin screw extruder.Extruder temperature is 200～240 ℃, and the pelletizing through extruding, after tie rod, water-cooled obtains the modified PET copolyesters P11 that high viscosity, low terminal carboxy content, hot water resistance can be good.
Embodiment 2: the preparation of the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good
By 1Kg P2,8g1, after two (2-oxazolinyl) benzene of 3-, 9g ADR-4370S mix in high-speed mixer, drops in twin screw extruder.Extruder temperature is 200～240 ℃, and the pelletizing through extruding, after tie rod, water-cooled obtains the modified PET copolyesters P12 that high viscosity, low terminal carboxy content, hot water resistance can be good.
Embodiment 3: the preparation of the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good
By 1Kg P3,50g1, after two (2-oxazolinyl) the benzene master batches of 3-, 11g '-diphenylmethane diisocyanate mix in high-speed mixer, drops in twin screw extruder.Extruder temperature is 200～240 ℃, and the pelletizing through extruding, after tie rod, water-cooled obtains the modified PET copolyesters P13 that high viscosity, low terminal carboxy content, hot water resistance can be good.
Embodiment 4: the preparation of the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good
By 1Kg P4, after 18g2-oxazolinyl benzene, 20g tolylene diisocyanate mix in high-speed mixer, drop in twin screw extruder.Extruder temperature is 200～240 ℃, and the pelletizing through extruding, after tie rod, water-cooled obtains the modified PET copolyesters P14 that high viscosity, low terminal carboxy content, hot water resistance can be good.
Embodiment 5: the preparation of the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good
By 1Kg P5,20g2,2-is two-after 2-oxazoline, 14g toluene isofoer diisocyanate mix in high-speed mixer, drops in twin screw extruder.Extruder temperature is 200～240 ℃, and the pelletizing through extruding, after tie rod, water-cooled obtains the modified PET copolyesters P15 that high viscosity, low terminal carboxy content, hot water resistance can be good.
Embodiment 6: the preparation of the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good
By 1Kg P6,50g1, after two (2-oxazolinyl) the benzene master batches of 3-, 20g ADR-4300 mix in high-speed mixer, drops in twin screw extruder.Extruder temperature is 200～240 ℃, and the pelletizing through extruding, after tie rod, water-cooled obtains the modified PET copolyesters P16 that high viscosity, low terminal carboxy content, hot water resistance can be good.
Embodiment 7: the preparation of the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good
By 1Kg P7,16g2,2-is two-after 2-oxazoline, 16g carbodiimide mix in high-speed mixer, drops in twin screw extruder.Extruder temperature is 200～240 ℃, and the pelletizing through extruding, after tie rod, water-cooled obtains the modified PET copolyesters P17 that high viscosity, low terminal carboxy content, hot water resistance can be good.
Embodiment 8: the preparation of the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good
By 1Kg P8,9g1, after two (2-oxazolinyl) benzene of 3-, 10g hexamethylene diisocyanate mix in high-speed mixer, drop in twin screw extruder.Extruder temperature is 200～240 ℃, and the pelletizing through extruding, after tie rod, water-cooled obtains the modified PET copolyesters P18 that high viscosity, low terminal carboxy content, hot water resistance can be good.
Embodiment 9: the preparation of the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good
By 1Kg P9,14g2,2-is two-after 2-oxazoline, 13g hexamethylene diisocyanate mix in high-speed mixer, drops in twin screw extruder.Extruder temperature is 200～240 ℃, and the pelletizing through extruding, after tie rod, water-cooled obtains the modified PET copolyesters P19 that high viscosity, low terminal carboxy content, hot water resistance can be good.
Comparative example 1
By 1Kg P5,8g2, after 2-pair-2-oxazoline mixes in high-speed mixer, drop in twin screw extruder.Extruder temperature is 200～240 ℃, the pelletizing through extruding, after tie rod, water-cooled, both copolyesters Prf1.
Comparative example 2
After 1Kg P5,8g hexamethylene diisocyanate are mixed in high-speed mixer, drop in twin screw extruder.Extruder temperature is 200～240 ℃, the pelletizing through extruding, after tie rod, water-cooled, both copolyesters Prf2.
The copolyesters that embodiment 1～9 and comparative example 1～2 are prepared carries out performance measurement, the results are shown in Table 2.
From table 2, the modified PET copolyesters limiting viscosity that high viscosity of the present invention, low terminal carboxy content, hot water resistance can be good increases, content of carboxyl end group reduces, and MF1/MF0 value reaches 53% than comparative example reduction, and hot water resistance can be significantly improved.
The performance index of table 2 modified PET copolyesters
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a modified PET copolyesters, is characterized in that comprising following component by weight:
100 parts of low viscosity PET copolyesters;
0.8～2.0 part of oxazoline compounds;
0.6～2.0 part of hydroxyl chainextender.
2. modified PET copolyesters according to claim 1, is characterized in that: described low viscosity PET copolyesters is polyethylene terephthalate-co-ethylene glycol adipate(EGA).
3. modified PET copolyesters according to claim 2, is characterized in that: in described polyethylene terephthalate-co-ethylene glycol adipate(EGA), the weight ratio of polyethylene terephthalate unit and polyethylene glycol adipate unit is (0.8～1.0): 1.
4. modified PET copolyesters according to claim 1, is characterized in that: the limiting viscosity of described low viscosity PET copolyesters is 0.6～0.8dL/g.
5. modified PET copolyesters according to claim 1, is characterized in that: Suo Shu oxazoline compounds is 2,2-pair-2-oxazoline, 1, at least one in two (2-oxazolinyl) benzene of 3-and 2-oxazolinyl benzene.
6. modified PET copolyesters according to claim 1, is characterized in that: described hydroxyl chainextender is at least one in isocyanate ester compound and derivative, Racemic glycidol ether compound and Racemic glycidol ester compound.
7. modified PET copolyesters according to claim 6, is characterized in that: described isocyanate ester compound comprises at least one in the tripolymer of the dimer of vulcabond, vulcabond and the vulcabond of Carbodiimide-Modified; Described Racemic glycidol ether compound is the multipolymer that comprises methyl propenoic acid glycidyl ether structure.
8. modified PET copolyesters according to claim 7, is characterized in that: at least one in described vulcabond nail phenylene diisocyanate, '-diphenylmethane diisocyanate, mphenylenedimethylim-vulcabond, isofoer diisocyanate, hexamethylene diisocyanate and the '-diphenylmethane diisocyanate that contains carbodiimide.
9. one kind according to the preparation method of the modified PET copolyesters described in claim 1～8 any one, it is characterized in that comprising following concrete steps: low viscosity PET copolyesters, oxazoline compounds, hydroxyl chainextender are dropped in twin screw extruder after mixing in mixing machine, in 200～240 ℃ melt extrude, tie rod, pelletizing, obtain the modified PET copolyesters that high viscosity, low terminal carboxy content, hot water resistance can be good.
10. the application in engineering plastics, wrapping material according to the modified PET copolyesters described in claim 1～8 any one.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105077898A (en) * | 2015-08-19 | 2015-11-25 | 树业环保科技股份有限公司 | PET non-woven fabric shopping bag and preparation method thereof |
| CN105085957A (en) * | 2015-09-17 | 2015-11-25 | 福建师范大学泉港石化研究院 | Method for preparing film by dissolving polyester fibers |
| CN107474493A (en) * | 2017-07-03 | 2017-12-15 | 涂志秀 | A kind of PBAT resins and preparation method thereof |
| US10094050B2 (en) | 2015-11-04 | 2018-10-09 | Industrial Technology Research Institute | Fiber and method of manufacturing the same |
| CN115161799A (en) * | 2022-07-04 | 2022-10-11 | 恒天嘉华非织造有限公司 | High-purity high-viscosity terylene regenerated fiber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027037A (en) * | 2008-05-08 | 2011-04-20 | 诺瓦蒙特股份公司 | Aliphatic-aromatic biodegradable polyester |
| CN102492267A (en) * | 2011-12-02 | 2012-06-13 | 金发科技股份有限公司 | Amylum category complete biodegradable material and preparation method thereof |
-
2013
- 2013-11-29 CN CN201310628445.XA patent/CN103665788B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027037A (en) * | 2008-05-08 | 2011-04-20 | 诺瓦蒙特股份公司 | Aliphatic-aromatic biodegradable polyester |
| CN102492267A (en) * | 2011-12-02 | 2012-06-13 | 金发科技股份有限公司 | Amylum category complete biodegradable material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105077898A (en) * | 2015-08-19 | 2015-11-25 | 树业环保科技股份有限公司 | PET non-woven fabric shopping bag and preparation method thereof |
| CN105085957A (en) * | 2015-09-17 | 2015-11-25 | 福建师范大学泉港石化研究院 | Method for preparing film by dissolving polyester fibers |
| CN105085957B (en) * | 2015-09-17 | 2017-09-22 | 福建师范大学泉港石化研究院 | A kind of method of polyester fiber dissolving film |
| US10094050B2 (en) | 2015-11-04 | 2018-10-09 | Industrial Technology Research Institute | Fiber and method of manufacturing the same |
| US10100440B2 (en) | 2015-11-04 | 2018-10-16 | Industrial Technology Research Instittute | Polyester and method of manufacturing the same |
| CN107474493A (en) * | 2017-07-03 | 2017-12-15 | 涂志秀 | A kind of PBAT resins and preparation method thereof |
| CN115161799A (en) * | 2022-07-04 | 2022-10-11 | 恒天嘉华非织造有限公司 | High-purity high-viscosity terylene regenerated fiber and preparation method thereof |
| CN115161799B (en) * | 2022-07-04 | 2023-03-24 | 恒天嘉华非织造有限公司 | High-purity high-viscosity terylene regenerated fiber and preparation method thereof |
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